JP2002080767A - Active energy ray-curable water-based ink composition for ink-jet printing use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable water-based ink composition for ink-jet printing use having excellent adherence to various to-be-printed matters, abrasion resistance and water resistance, slight in odor and skin irritancy, and having good issue stability. SOLUTION: This water-based ink composition essentially comprises a colorant, an active energy ray-curable component, a water-miscible organic solvent and water; wherein the active energy ray-curable component is a water- based compound having in the molecule unsaturated double bond-bearing groups and carboxy group neutralized with a basic compound, especially being a polyurethane compound, and the total amount of the unsaturated double bond-bearing groups is preferably 1.0-5.0 equivalent/kg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous ink composition for ink jet recording, and
The present invention relates to an active energy ray-curable water-based ink composition for ink jet recording, which is excellent in abrasion resistance, water resistance, light resistance and the like, and has low odor and skin toxicity.

[0002]

2. Description of the Related Art Printing by an ink jet recording apparatus is performed by:
This is a method in which ink is ejected from a nozzle and adheres to a recording material, and the nozzle and the recording material are in a non-contact state.
Good printing can be performed on a curved surface or a surface having an irregular irregular shape. Therefore, this printing method is expected to be used in a wide range of fields.

[0003] As the ink used in such an ink jet recording apparatus, an aqueous ink using water as a main solvent and an oil-based ink using an organic solvent as a main solvent are generally used. Compared to oil-based inks, printed images using water-based inks are generally inferior in water resistance, but oil-based inks have problems in safety, odor, etc., whereas water-based inks have water as the main solvent. Because it is excellent in safety,
A water-based ink is generally used for the ink jet recording system.

However, such water-based inks have problems such as poor adhesion of printed images, abrasion resistance, and water resistance, and the use of a pigment as a coloring material as an ink to improve these problems has occurred. Ink with improved water and light resistance,
Many inks that have been improved in durability by being cured by active energy rays have been proposed.

As an ink jet recording ink which is cured by an active energy ray, for example, JP-A-3-216379
JP, JP-A-7-224241, JP-A-8-2180
In JP-A-16, an ink containing a coloring material, a water-soluble resin, a water-insoluble active energy ray-curable monomer, or a water-soluble active energy ray-curable monomer, a water-soluble organic solvent, and water as main components is proposed. JP-A-48922 proposes an aqueous ink containing a radiation-curable macromer in an emulsion state.

However, the inks described in JP-A-3-216379 and the like use only monomers as active energy ray-curable compounds, and it is difficult to achieve both curability and adhesion. That is, when a monomer having a large number of functional groups is used, the volume shrinkage becomes large and the adhesion is reduced. When a monomer having a small number of functional groups is used, the adhesion is improved but the curability is reduced. Further, there are problems in safety and hygiene such as odor due to volatilization of the low boiling point monomer and skin toxicity due to contact.

[0007] Further, in the ink described in JP-A-8-48922, when moisture evaporates, emulsion particles are destroyed and a film is formed on the end face of the nozzle. In this case, since a macromer that is substantially insoluble in water is used, the resolubility of the formed ink film by water is insufficient, and insoluble matter adheres and accumulates at the discharge port, and the discharge stability is reduced. Is insufficient.

Further, the ink jet recording system is mainly used for an ink-absorbing recording material such as paper, and has good adhesion, abrasion resistance, water resistance and the like to a recording material having no ink absorption. At present, there is no aqueous ink for inkjet recording which has good discharge stability.

[0009]

The problem to be solved by the present invention is that excellent ink adhesion, abrasion resistance, water resistance, light resistance, etc., which are problems in conventional ink-jet inks, odor, skin irritation, etc. An object of the present invention is to provide an active energy ray-curable water-based ink for inkjet recording, which has no ink jetting property and excellent ejection stability. In particular, the present invention provides an active energy ray-curable water-based ink for ink jet recording, which is capable of printing with good adhesion, abrasion resistance, and water resistance to a recording material having no ink absorbency, capable of forming an image, and having excellent ejection stability. It is in.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a lipophilic active energy ray-curable compound containing a group having an unsaturated double bond can be obtained. An aqueous compound prepared by a method for introducing a polar group (carboxyl group) into a molecule is dissolved or dispersed in water together with a basic compound, and the content of the group having a double bond is in a specific range. By using it as an active energy ray-curable component of recording ink, it has good re-dissolvability, excellent adhesion of a cured film, excellent abrasion resistance, water resistance, light resistance, etc., less odor and skin irritation, and It has been found that a water-based ink for ink jet recording having excellent ejection stability can be obtained, and the present invention has been achieved.

That is, the present invention relates to a water-based ink composition for ink jet recording containing a coloring material, an active energy ray-curable component, a water-soluble organic solvent and water as main components. It is intended to provide an active energy ray-curable aqueous ink composition for inkjet recording, characterized by containing an aqueous compound having a group having a saturated double bond and a carboxyl group neutralized by a basic compound, and in particular, In an active energy ray-curable aqueous ink composition for inkjet recording containing a polyurethane compound containing a group having an active energy ray-curable unsaturated double bond, a basic compound, a colorant, a water-soluble organic solvent and water, The polyurethane compound has a carboxyl group and the sum of the groups having the double bond is 1.0 to 5 0 there is provided an active energy ray curable aqueous ink composition for ink-jet recording, which is a equivalent / kg. Since the active energy ray-curable aqueous ink composition for inkjet recording of the present invention does not use an active energy ray-curable monomer, there is no danger of odor due to volatilization of the monomer or contact with the skin. Further, the aqueous polyurethane compound used as the active energy ray-curable component in the present invention is more easily compatible with the curability and adhesion of the film than the active energy ray-curable monomer. That is, a group having an active energy ray-curable unsaturated double bond is added in an amount of 1.0 to 5.0.
By setting the equivalent weight / kg, it is possible to obtain an aqueous ink composition for ink jet recording having excellent curability, low volume shrinkage and excellent adhesion.

Next, the present invention will be described in detail. The group having an unsaturated double bond in the active energy ray-curable component used in the present invention is composed of a methacryloyl group and an acryloyl group, and in order to obtain sufficient active energy ray curability and excellent cured film performance, It is necessary that the sum of the groups having an unsaturated double bond is from 1.0 to 5.0 equivalents / kg, more preferably from 1.5 to 3.5 equivalents / kg.
It is desirable to set to. By having such a range, without containing an active energy ray-curable monomer for promoting the curing of the film in the aqueous ink composition,
Good film curability can be achieved. If it is less than 1.0 equivalent / kg, the curability becomes insufficient, and if it is more than 5.0 equivalent / kg, the volume shrinkage of the cured product becomes large,
Adhesion to the print is insufficient.

The carboxyl group neutralized with the basic compound in the aqueous polyurethane compound as the active energy ray-curable component used in the present invention has an effect on the resolubility of the aqueous compound and the water resistance of the cured film. To make them compatible,
The acid value is 20 to 80 KOH mg / g, preferably 30 to 6
Desirably, it is 0 KOHmg / g.

As described above, as the active energy ray-curable component used in the ink for ink-jet recording, those having good resolubility are preferable. Generally, the lower the molecular weight is, the better the resolubility is, but the performance of the cured film is reduced. Active energy ray-curable aqueous compounds include polyesters, polyethers, polyurethane compounds, and the like.Polyurethane compounds have highly polar urethane bonds, so even relatively small molecules can be entangled with molecules similar to polymers by hydrogen bonds. As a result, excellent coating performance can be obtained. Therefore, it is possible to obtain an ink having good re-dissolving property and excellent coating performance. For this reason, it is preferable to use an aqueous polyurethane compound.

An aqueous polyurethane compound having a group having an unsaturated double bond in a molecule and a carboxyl group neutralized with a basic compound (hereinafter, referred to as a "polyurethane") can be used in the present invention.
The active energy ray-curable aqueous polyurethane compound) can be obtained, for example, by the following procedure.

First, an isocyanate group-terminated urethane prepolymer obtained by reacting a compound (A) having two or more active hydrogens with a compound (B) having a carboxyl group and a polyisocyanate compound (C), A hydroxy (meth) acrylate (D) having 1 to 2 hydroxyl groups and 1 to 5 methacryloyl groups or acryloyl groups therein is reacted. Here, 0 to 80% of the compound (A) having two or more active hydrogens is polyhydroxy (meth)
It can be acrylate (al). In the text of the present invention, a compound having a methacryloyl group and an acryloyl group in a molecule is hereinafter referred to as (meth) acrylate.

These reactions can be carried out at 20 to 80 ° C. by adding a solvent which does not react with isocyanate, and known polymerization inhibitors and reaction catalysts can be arbitrarily added in appropriate amounts.
The carboxyl group of the organic solvent solution after completion of the reaction is neutralized with a basic compound at 5 to 50 ° C., water is added at 5 to 40 ° C., and the reaction solvent is recovered by distillation at 50 to 60 ° C. under reduced pressure. An active energy ray-curable aqueous polyurethane compound is obtained.

In the above reaction, the molar ratio of the isocyanate group-terminated urethane prepolymer to the hydroxy (meth) acrylate (D), that is, the equivalent of the active hydrogen to be reacted with the isocyanate group may be 5/1 to 1/1 if necessary. Can be determined arbitrarily.

The active energy ray-curable aqueous polyurethane compound which can be used in the present invention comprises (A)
When the isocyanate-terminated urethane prepolymer obtained by reacting (B) and (C) with hydroxy (meth) acrylate was set to have an excess of isocyanate groups, the carboxyl groups were neutralized and water was added. Thereafter, the isocyanate group can be cross-linked or chain-extended with a polyamine compound, a ketimine compound, or water.

The compound (A) having two or more active hydrogens is selected from polyol resins having a number average molecular weight of 300 to 5,000, such as polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyether polyols, polyester polyether polyols and polybutadiene polyols. A polyol component comprising at least one kind of polyol resin selected from a group and another polyol can be exemplified.

Typical examples of other polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 2-methyl-1.3-propanediol as a diol component or a compound having an equivalent effect. , Dipropylene glycol, 1.3-butylene glycol, 1.4
-Butylene glycol, neopentyl glycol, 1.
6-hexanediol, 3-methyl-1.5-pentanediol, 2-ethyl-1.3-hexanediol, 2
-Butyl-2-ethyl-1.3 propanediol, cyclohexane-1.4-dimethanol, and spiroglycols.

Next, as the polyol component having a valency of 3 or more,
Examples thereof include polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polybutadiene polyol, and polypentadiene polyol, or compounds having an equivalent effect.

Polyhydroxy (meth) acrylate (a
Examples of l) include dihydroxymono (meth) acrylates such as glycerin mono (meth) acrylate, and compounds obtained by addition-polymerizing ethylene oxide, propylene oxide, and tetrahydrafuran. Further, 2-methacryloyloxyethylene isocyanate,
By reacting a product obtained by reacting methacryloyl isocyanate with dialkanolamine, or a diisocyanate having two isocyanate groups having different reactivities with monohydroxymono (meth) acrylate, monohydroxydi (meth) acrylate, etc. A product obtained by reacting the obtained half urethane (meth) acrylate with a dialkanolamine can also be mentioned as a typical example.

Representative diisocyanates having two isocyanate groups having different reactivities include isophorone diisocyanate and tolylene diisocyanate.

Representatives of alkanolamines include diethanolamine, diisopropanolamine, dipropanolamine, dibutanolamine and the like.

As the compound (B) having a carboxyl group, diols and amines are suitable. As specific examples, diaminocarboxylic acids such as lysine, cystine and 3.5-
Obtained by reacting diaminocarboxylic acid, 2.6-dihydroxybenzoic acid and especially dihydroxyalkanoic acids such as 2.2-dihydroxypropionic acid, 2.2 dihydroxybutanoic acid and 2.2-dihydroxypropionic acid with ε-caprolactone. Carboxyl group-containing polycaprolactone diol, etc.

Specific examples of the polyisocyanate compound (C) include ethylene diisocyanate, 1.
6-hexamethylene diisocyanate, 2.2.4-trimethylhexamethylene diisocyanate, 2.4.4
Aliphatic triisocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane
4.4-diisocyanate, 1.3-bis (isocyanatomethyl) cyclohexane, norbornanediisocyanatomethyl, isopropylidenedicyclohexyl-
Examples thereof include alicyclic diisocyanates such as 4.4'-diisocyanate and diisocyanates such as aromatic diisocyanates such as 4.4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and tolylene diisocyanate.

Further, an adduct of the above-mentioned diisocyanate polymer or a diisocyanate with a polyol such as trimethylolpropane or ethylene glycol;
Alternatively, urea-modified, burette-modified, carbodiimide-modified, uretonimine-modified, allohanate-modified diisocyanate and the like are applicable.

Representative examples of hydroxy (meth) acrylate (D) having 1 to 2 hydroxyl groups, 1 to 5 methacryloyl groups and acryloyl groups in the molecule include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (D). Monohydroxy mono (meth) acrylates such as meth) acrylate and hydroxybutyl (meth) acrylate; or monohydroxy methacrylates such as glycerin di (meth) acrylate, biscoat 214HP (manufactured by Osaka Organic Co., Ltd.), and pentaerythritol triacrylate. Dihydroxymono (meth) acrylates such as monohydroxytriacrylate, dipentaerythritol pentaacrylate, and glycerin mono (meth);
And compounds obtained by addition polymerization of ethylene oxide, propylene oxide, and tetrahydrofuran.

Further, a compound obtained by reacting a polyfunctional acrylate with a dialkanolamine or a monoalkylmonoalkanolamine by a Michael addition reaction, or a diisocyanate having two isocyanate groups having different reactivities and a monohydroxymonoacrylate or monohydroxydi ( A typical example of (D) is a product obtained by reacting half urethane obtained by a reaction with (meth) acrylate or the like, or methacryl isocyanate with a dialkanolamine or a monoalkylmonoalkanolamine.

As the above polyfunctional (meth) acrylate, one or more polyfunctional acrylates such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and glycerin monoacrylate dimethacrylate can be used. Having a methacryloyl group and at least one acryloyl group.

Representative examples of diisocyanates having two isocyanate groups having different reactivities include isophorone diisocyanate and tolylene diisocyanate.

Representatives of dialkanolamine include diethanolamine, diisopropanolamine, dipropanolamine, dibutanolamine and the like.

Representative examples of the monoalkylmonoalkanolamine include methylethanolamine, ethylethanolamine, methylpropanolamine and the like.

The reaction temperature is preferably in the range of 20 to 80 ° C. The reaction solvent may be an organic solvent which does not react with isocyanate during the reaction or after the reaction. Examples of these organic solvents include acetone, methyl ethyl ketone, tetrahydrofuran, N-methylpyrrolidone, ethyl acetate and the like. In addition, to prevent polymerization of double bonds, commonly used polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tertiary butyl hydroquinone, and phenothiazine are added to accelerate the reaction between hydroxyl groups and isocyanate groups as necessary. A reaction catalyst such as dibutyltin laurate, stannas octoate, triethylamine and the like can be used.

Examples of the basic compound for neutralizing a carboxyl group include triethylamine, trimethylamine, dimethylmonoethanolamine, diethylethanolamine,
Tertiary amines such as diethanol monomethylamine and triethanolamine are exemplified.

The content of the aqueous urethane compound in the active energy ray-curable aqueous ink composition for ink-jet recording is determined by considering the viscosity of the ink and the durability of the printed image.
A range of from 20 to 20% by mass is preferred.

As the active energy ray-curable component, a conventionally known active energy ray-curable monomer can be used in combination. However, depending on the monomer,
Some of them have an odor or irritate the skin, so it is desirable not to use them.

The active energy ray-curable aqueous ink composition for ink jet recording of the present invention comprises a coloring material, an active energy-curable component, a water-soluble organic solvent, and water, and optionally contains an auxiliary.

As the coloring material, dyes and pigments generally used in ink jet recording inks can be used. As the dye, for example, an azo dye as a direct dye, a phthalocyanine dye, an azo dye as an acid dye,
And anthraquinone dyes.

In order to impart excellent water resistance and light resistance to a printed image, it is preferable to use a pigment, and all conventionally known organic pigments and inorganic pigments can be used. Specifically, azo pigments, phthalocyanine pigments, perylene pigments,
Organic pigments such as quinacridone pigments and isoindoline pigments,
Examples include inorganic pigments such as titanium oxide and carbon black, but are not limited thereto.

These coloring materials can be used alone or in combination of two or more. The content of the coloring material in the ink composition is 0.1 to 10 in order to obtain good film strength and coloring.
The range of mass% is preferred.

The water-soluble organic solvent is used to prevent the solidification of the ink due to the evaporation of water, to ensure resolubility in water and ink even when solidified, and to prevent the ink from penetrating into the ink-absorbing recording material. Used for shortening. Specifically, ethylene glycol, diethylene glycol,
Glycols such as polyethylene glycol and glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, glycol ethers such as ethylene glycol monophenyl ether, pyrrolidones such as N-methyl-2-pyrrolidone, Examples thereof include alkanolamines such as triethanolamine, alcohols such as methanol, ethanol, and isopropyl alcohol, and dimethyl sulfoxide.

These water-soluble organic solvents may be used alone or in combination of two or more in consideration of the hygroscopicity and moisture retention of the solvent, the solubility of the dye, the dispersibility of the pigment, the viscosity of the ink and the time of penetration into the recording material. Can be used in combination. The content of the water-soluble organic solvent is preferably from 30 to 150% by weight, and more preferably from 40 to 80% by weight, based on the content of the active energy ray-curable compound.
The range of weight% is more preferred. If the amount of the water-soluble organic solvent with respect to the active energy ray-curable compound is less than the above range, clogging due to evaporation of water at the nozzle end surface is likely to occur, and if the amount is too large, the strength and water resistance of the cured film decrease. The amount used in the ink composition is preferably from 2 to 30% by mass in terms of clogging, film strength, and water resistance.

As the water, it is desirable to use water having a purity higher than that of ion-exchanged water in order to stabilize the dissolution of the dye and prevent nozzle clogging due to heavy metal ions. The amount used in the ink composition is generally in the range of 40 to 90% by mass.

As an auxiliary agent, hydroxides of alkali metals, pH adjusters such as alkanolamines, germicides, fungicides, sequestering agents, pigment dispersants, water-soluble resins and the like may be used. .

Further, a photopolymerization initiator can be used if necessary. However, when a high energy ray such as an electron beam is used as the active energy ray, the photopolymerization initiator does not need to be particularly used. . As the active energy ray, it is preferable to use ultraviolet rays from the viewpoint of safety and simplicity.

The photopolymerization initiator is soluble in water or the water-soluble organic solvent used in the present invention, is present in the ink in a stable manner, and radicals generated by ultraviolet rays are converted into active energy ray-curable aqueous urethane compounds. Any substance that efficiently reacts with the unsaturated double bond therein can be used. Specifically, benzoin compounds such as benzoin ethyl ether and benzoin isopropyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Examples include acetophenone-based compounds such as (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, benzophenone-based compounds such as benzophenone, and thioxanthone-based compounds, but are not limited thereto. More than one kind can be used together.
The use amount of these photopolymerization initiators is usually 0.1 to 20% by mass based on the active energy curable component. Further, photoinitiating aids such as triethanolamine and methyldiethanolamine can also be used.

[0049]

The present invention will be described below in detail with reference to examples. In the following description, "parts" represents parts by mass.

Preparation Example 1 A reactor equipped with a stirrer equipped with a reflux condenser, an air introduction pipe, and a thermometer was charged with Placcel L.
205AL (molecular weight 500, lactone polyester diol manufactured by Daicel Chemical Industries, Ltd.) 35.9 parts, dimethylolpropionic acid 20.4 parts, trimethylolpropane 4.53 parts, butylethylpropanediol 10.1
Part, 2.5 of polyethylene glycol PEG # 600
Parts, 87.4 parts of 1.3-bis (isocyanatomethyl) cyclohexane, 24.1 parts of N-methylpyrrolidone, 136.7 parts of ethyl acetate, and 0.016 part of stannous octoate. To 0.5 ° C in 0.5 hours
After reacting at ~ 75 ° C for 5 hours, 0.14 parts of methquinone, NK
47.5 parts of Ester-701 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
0.07 parts of stannous octoate. Methyl ethyl ketone 9
5.7 parts were added and reacted again at 70 to 75 ° C. for 6 hours to obtain a solution of a polyester urethane resin skeleton. 50
C. and the solution was added with 15.4% triethylamine.
And 518.5 parts of pure water, gradually add
The mixture was kept at 0 minutes, 0.2 parts of Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) was added, and the mixture was distilled under reduced pressure at 50 ° C. to remove ethyl acetate and methyl ethyl ketone.
A composition having an active energy ray-curable aqueous urethane compound having 9.2% by mass, Gardner viscosity: + X, and transparent appearance was prepared. The characteristics of this urethane compound were as follows. Acryloyl group concentration: 0.0 equivalent / kg Methacryloyl group concentration: 1.858 equivalent / kg Acryloyl group / methacryloyl group equivalent ratio: 0/10
0 Solid content acid value: 41 KOHmg / g

(Preparation Example 2) Placcel L was placed in a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet, and a thermometer.
205AL (molecular weight 500, lactone polyester diol manufactured by Daicel Chemical Industries, Ltd.) 36.0 parts, dimethylolpropionic acid 20.5 parts, trimethylolpropane 4.54 parts, butylethylpropanediol 10.2 parts polyethylene glycol PEG # 2.54 parts of 600,
96.1 parts of norbornane diisocyanatomethyl (manufactured by Mitsui Toatsu Chemicals, Inc.), N-methylpyrrolidone 32.1
And 229.6 parts of ethyl acetate.
The temperature was raised to 0 ° C. in 0.5 hours, and after reacting at 70 to 75 ° C. for 5 hours, the nitrogen introducing tube was switched to an air introducing tube, and 0.18 parts of methquinone, biscoat # 214HP (manufactured by Osaka Organic Chemical Co., Ltd.) 44.3 parts) and 0.11 part of stannous octoate were added and reacted again at 70 to 75 ° C. for 6 hours to obtain a solution of a polyester urethane resin skeleton. After cooling to 50 ° C., 15.4 parts of triethylamine and 50 parts of pure water were added to the solution.
Add 8.6 parts gradually, keep at 35-40 ° C for 30 minutes,
Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.)
45 parts, and distilled under reduced pressure at 50 ° C. to remove ethyl acetate. Nonvolatile content: 29.6% by mass, Gardner viscosity:
A composition having an active energy ray-curable aqueous urethane compound having a QR and a transparent appearance was prepared. The characteristics of this urethane compound were as follows. Acryloyl group concentration: 0.911 equivalent / kg Methacryloyl group concentration: 0.911 equivalent / kg Acryloyl group / methacryloyl group equivalent ratio: 100/1
00 Solid content acid value: 40 KOHmg / g

(Example 1) Carbon black # 45L
(Mitsubishi Chemical) 20 parts, dispersant Solspers 27000
Using 6 parts of (Zeneca), 0.75 parts of Solspers 12000 (Zeneca), and 73.25 parts of purified water as media, 450 parts of zirconia beads having a diameter of 1.2 μm were dispersed with a paint conditioner for 3 hours to prepare carbon black. An aqueous dispersion was obtained. To 20 parts of this aqueous dispersion, 40 parts of the active energy ray-curable aqueous polyurethane composition of Preparation Example 1, 5 parts of purified glycerin (manufactured by Kao), and Darocur 1173 (manufactured by Ciba Specialty Chemical) as a photopolymerization initiator. 2 parts, TSF4452 as surfactant
(Toshiba Silicone Co., Ltd.) and 35 parts of purified water were added, mixed with stirring, and filtered using a 1.2 μm membrane filter to obtain an ultraviolet-curable aqueous jet ink.

The obtained ink is drained and washed.
Dry Epson printer PM-670C cartridge
To a jet printer.
Paper printed on Kao paper and PET film
As a result, the ejection stability is good and a clear printed image can be obtained.
Was. The obtained printed matter is put in a nitrogen atmosphere at 120 w / cm. ^Two
Using a metal halide lamp (made by Ushio Inc.)
Irradiation with line, 1J / cm^TwoCured with the energy of
The following adhesion, abrasion resistance and water resistance tests were performed.

"Adhesion test" The printed matter on the PET film was visually evaluated for the presence or absence of peeling of the printed image in a peeling test using "Cellotape" (cellophane adhesive tape manufactured by Nichiban Co., Ltd.).

"Abrasion resistance test" A rubbing tester was used to rub a printed portion 100 times with felt on a special paper for a jet printer and a PET film with a load of 0.5 kg / cm2, and the presence or absence of peeling of the printed image was visually evaluated. did.

"Water resistant" special paper for jet printers,
With respect to the PET film, the presence or absence of peeling of the printed image after 24 hours of the printed matter in tap water and a decrease in the density of the printed image were visually evaluated.

As a result of the above test, the abrasion resistance and water resistance of the special paper for jet printers were good.
Adhesion to PET film, abrasion resistance and water resistance were also good.

Example 2 "BONJ" manufactured by Orient Chemical
20 parts of "ET BLACK CW-1" (water dispersion of carbon black), 40 parts of the active energy ray-curable aqueous polyurethane composition of Preparation Example 2, purified glycerin 7.5
Parts, 1.2 parts of Darocur 1173 as a photopolymerization initiator
Parts, 0.2 part of TSF4452 as a surfactant and 32.5 parts of purified water were stirred and mixed, and filtered using a 1.2 μm membrane filter to obtain an ultraviolet-curable aqueous jet ink.

The obtained ink was filled in an Epson Preowner PM-670C cartridge in the same manner as in Example 1, and the same printer was used to print on a jet printer paper (manufactured by Kao) and a PET film. The stability was good, and a clear printed image was obtained.

The printed matter was cured with ultraviolet rays in the same manner as in Example 1, and the adhesion, abrasion resistance and water resistance of the printed image were tested in the same manner as in Example 1. As a result, the printed matter was resistant to jet printer paper. The abrasion and water resistance were good, and the adhesion to the PET film, abrasion resistance and water resistance were also good.

(Comparative Adjustment Example) A reactor equipped with a stirrer equipped with a reflux cooling pipe, an air introduction pipe, and a thermometer was charged with Praxel L205AL (molecular weight 500, Daicel Chemical Industries, Ltd.).
Lactone polyester diol) 50.3 parts, dimethylolbutanoic acid 20.8 parts, trimethylolpropane 4.49 parts, butylethylpropanediol 10.7
Part, 2.5 of polyethylene glycol PEG # 600
Parts, 89.5 parts of 1.3-bis (isocyanatomethyl) cyclohexane, 178.2 parts of methyl ethyl ketone, and 0.01 part of stannous octylate, and the mixture was heated to 70 ° C. in 0.5 hour with stirring. After reacting at 70 ° C. to 75 ° C. for 5 hours, 0.14 part of methoquinone, 20.4 parts of β-hydroxyethyl acrylate, and 0.01 part of stannous octoate. 0.15 parts of methoquinone and 62.2 parts of methyl ethyl ketone were added, and the mixture was reacted again at 70 to 75 ° C for 6 hours to obtain a solution of a polyester urethane skeleton. After cooling to 50 ° C., 24.3 parts of acetonitrile and 14.4 parts of trimethylamine were added to the solution, and the mixture was stirred for 20 minutes. 516.4 parts of pure water was gradually added, and the mixture was kept at 35 to 40 ° C. for 30 minutes. 0.5 parts of NOL AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) was added thereto, and the mixture was distilled under reduced pressure at 50 ° C. to remove ethyl acetate and methyl ethyl ketone. The nonvolatile content was 29.4% by weight, the Gardner viscosity was + X, An active energy ray-curable aqueous urethane composition having a transparent appearance was prepared. Acryloyl group concentration: 0.8 equivalent / kg Methacryloyl group concentration: 0 kg Acryloyl group / methacryloyl group equivalent ratio: 0/10
0 Solid content acid value: 40 KOHmg / g

Comparative Example An ultraviolet-curable aqueous jet was prepared in the same manner as in Example 1 except that the active energy ray-curable aqueous polyurethane composition described in Comparative Example was used as the active energy ray-curable aqueous polyurethane composition. Ink was obtained. The obtained ink was filled in an Epson printer PM-670C cartridge in the same manner as in Example 1,
As a result of printing on a jet printer paper (manufactured by Kao) and a PET film using the same printer, the ejection stability was good and a clear printed image was obtained. However, the printed matter was cured by ultraviolet rays in the same manner as in Example 1,
In the same manner as in Example 1, adhesion of printed images, abrasion resistance,
When a water resistance test was carried out, satisfactory characteristics were not obtained due to poor curing, and the characteristics for a PET film in particular did not reach a practical level at all.

According to the present invention, an aqueous compound having a group having an unsaturated double bond in a molecule and a carboxyl group neutralized with a basic compound is used as an active energy ray-curable component in an ink. Thus, an active energy ray-curable aqueous ink composition for inkjet recording having excellent adhesion, abrasion resistance, water resistance, etc., low odor and skin irritation, and excellent discharge stability was prepared.

Continued on the front page F term (reference) 2C056 EA13 FC01 HA44 2H086 BA53 BA59 BA62 4J039 AE04 BA12 BC07 BC08 BC09 BC10 BC11 BC13 BC14 BC15 BC35 BC50 BC54 BC74 BC75 BE01 BE02 BE12 CA03 EA04 EA35 EA36 EA38 EA43 GA24

Claims (3)

[Claims] An active energy ray-curable aqueous ink for inkjet recording comprising a polyurethane compound containing a group having an active energy ray-curable unsaturated double bond, a basic compound, a colorant, a water-soluble organic solvent and water. In the composition, the polyurethane compound has a carboxyl group and the sum of the groups having a double bond is from 1.0 to 5.0 equivalents / kg, for active energy ray-curable inkjet recording. Aqueous ink composition. 2. An acid value of the polyurethane compound is 20 to 20.
2. The active energy ray-curable water-based ink composition for ink jet recording according to claim 1, wherein the water-based ink composition is 80. 3. The active energy ray-curable inkjet recording method according to claim 1, wherein the content of the water-soluble organic solvent is 30 to 150% by weight based on the content of the polyurethane compound. Aqueous ink composition.